WO1996025481A1 - Solid detergent block - Google Patents

Solid detergent block Download PDF

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Publication number
WO1996025481A1
WO1996025481A1 PCT/EP1996/000323 EP9600323W WO9625481A1 WO 1996025481 A1 WO1996025481 A1 WO 1996025481A1 EP 9600323 W EP9600323 W EP 9600323W WO 9625481 A1 WO9625481 A1 WO 9625481A1
Authority
WO
WIPO (PCT)
Prior art keywords
weight
builder
block
ingredient
compressing
Prior art date
Application number
PCT/EP1996/000323
Other languages
English (en)
French (fr)
Inventor
Guido Clemens Van Den Brom
Seeng Djiang Liem
Harmannus Tammes
Original Assignee
Unilever N.V.
Unilever Plc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=8220022&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO1996025481(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Unilever N.V., Unilever Plc filed Critical Unilever N.V.
Priority to JP52460496A priority Critical patent/JP3833252B2/ja
Priority to CA002211229A priority patent/CA2211229C/en
Priority to BR9607331A priority patent/BR9607331A/pt
Priority to EP96901771A priority patent/EP0809689B1/en
Priority to AU46218/96A priority patent/AU713237B2/en
Priority to DE69602086T priority patent/DE69602086T2/de
Publication of WO1996025481A1 publication Critical patent/WO1996025481A1/en
Priority to FI973347A priority patent/FI973347A0/fi

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Classifications

    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02Inorganic compounds ; Elemental compounds
    • C11D3/04Water-soluble compounds
    • C11D3/08Silicates
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0047Detergents in the form of bars or tablets
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/26Organic compounds containing nitrogen
    • C11D3/33Amino carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16Organic compounds
    • C11D3/37Polymers
    • C11D3/3703Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3707Polyethers, e.g. polyalkyleneoxides

Definitions

  • the present invention relates to a solid detergent block for obtaining an aqueous chemical solution having a substantially constant concentration.
  • the invention also relates to a process for preparing such a block.
  • Such detergent blocks are suitable for use in an industrial cleaning process, particularly a mechanical arewashing process and generally comprise alkaline agents and deter- gency builders.
  • Industrial ware washing machines generally comprise a wash tank which contains the cleaning solution for the wash process.
  • the soiled wash load is doused with the cleaning solution and subsequently with rinse water which falls into the wash tank.
  • the cleaning power of the cleaning liquor is reduced, first because some is exhausted by the soil-removing process and, secondly, because it is diluted with rinse water.
  • the cleaning solution is therefore recharged from time to time by adding fresh cleaning product from a dispenser system, which usually provides liquid product or a concentrated aqueous solution of a composition including solid chemicals.
  • a solid powdered chemical can be dissolved by placing it on a sieve and spraying water on to said sieve from below.
  • the powdered material can be dissolved in a dispenser of the "water-in-reservoir" type. In this type of dispenser, the powdered material is submerged under water, which therefore becomes loaded or even saturated with the powder. When more water is added, the excess solution flows into an overflow pipe leading to the washing machine.
  • briquettes such as, for instance, described in US patents 2,382,163, 2,382,164 and 2,382,165. Briquettes can be used with a "water-in-reservoir" type of dispenser.
  • a well-known type of solid detergent is the cast block form, whereby a solid detergent block having a weight of several kilograms is formed by pouring a concentrated aqueous slurry into a container, in which it solidifies upon cooling as a result of the hydration of the salts in the composition.
  • Such cast solid blocks are, for example, described in European patent 3,769.
  • Solid detergent blocks have won a certain degree of popularity in the area of industrial warewashing because they constitute a non-dusty and therefore relatively safe product form for the often aggressive chemicals used. Furthermore, hydrated solid blocks are economical in use because they can be manufactured and transported as con ⁇ centrated products. However, elevated temperatures are required in the manufac ⁇ turing process of the above-mentioned solid detergent blocks and these temperatures have an adverse effect on the stability of heat-labile components of the blocks.
  • EP-A-375,022 an alternative type of detergent block is disclosed, namely a block of compressed granular material. This block constitutes an even more concentrated product and enables the incorporation of heat-labile components such as bleach compounds.
  • a good quality detergent block is defined as a block having a bulk density of 1200-2100 kg/m 3 and showing neither cracks in the block (lamination) nor at the top or bottom surface of the block (capping) .
  • a block which is substantially free of phosphate builder is defined as a block not containing more than 1% by weight of phosphorus.
  • a process for preparing a block of compressed granular material being substantially free of a phosphate builder and having a weight of 0.2 to 10 kg, said process involving the steps of
  • Another aspect of the invention is a solid detergent com ⁇ position in the form of a block of a compressed granular material, said block having a weight of 0.2-10 kg, being substantially free of a phosphate builder and comprising:
  • a compressing aid selected from nonionic surfactants, metal soaps, paraffins, talcum pow- der, polyethylene glycol, mixtures of ketones and fatty alcohols, and mixtures thereof;
  • detergent blocks having a porosity of at most 10% by volume and a bulk density of 1200-2100 kg/m 3 , preferably 1500-1900 kg/m 3 , can be prepared.
  • said blocks do preferably not contain any phosphate builder.
  • the detergent blocks of the invention have a weight of 0.2- 10 kg, preferably 1-5 kg.
  • the blocks are usable for various applications in the area of industrial cleaning, such as mechanical warewashing and fabric washing, but other in- dustrial detergent processes are also envisaged (e.g. bottle washing or conveyor belt lubricating) .
  • the blocks are particularly suitable for use in a mechanical ware washing process.
  • the detergent blocks of the invention generally contain detergent components usually found in material suitable for use in an industrial washing machine, such as a detergency builder, an alkaline agent, a bleaching agent and one or more types of foam-depressing and lubricating material.
  • non-phosphate builder material is granulated with 0.1-10% by weight based on the weight of the builder of a co-ingredient selected from polycarboxylic polymer solutions, alkali metal silicate solutions, and mixtures thereof.
  • the granulation step is preferably carried out by dry- mixing the builder with the co-ingredient, desirably at room temperature. This may be effectively performed in a Loedige or Fukae type batch or continuous mixer.
  • the builder material may be granulated by forming a slurry containing said builder and the co- ingredient and subsequently spray-drying the slurry. If needed, the thus obtained granulated builder material may be dried in a fluid bed to a free moisture content of less than 5% by weight, preferably less than 3% by weight (measured at 120°C) . It was observed that the compac- tibility of the particulate mixture used for preparing the detergent block of the invention could be improved by applying the above described drying step.
  • Suitable polycarboxylated polymers for use as co-ingredient are selected from the group consisting of homopolymers and copolymers of one or more of acrylic acid, methacrylic acid, maleic acid, acrylamide, itaconic acid, (C,-C 4 ) -alkyl (meth) -acrylates or amides, alpha-chloroacrylic acid, alkyl-vinylether or vinylesthers. Most preferred polymers are selected from the group of homopolymers and copolymers of acrylic acid and maleic acid.
  • alkali metal silicate solution is preferred for use as co-ingredient since this material can be used at much lower levels (i.e. 0.25-5%, preferably 0.5-3.0% by weight based on the weight of the non-.phosphate builder) than the polycarboxylated polymer owing to its lower viscosity.
  • the viscosity of the silicate solution is lower than 400 mPas at 20°C whereas the viscosity of the polycarboxylated polymer solution is generally considerably higher.
  • sodium silicate containing silicium oxide and sodium oxide at a weight ratio in the range of 1.0 - 3.3, especially of 1.5 - 2.2, is applied.
  • the compressing aid is selected from nonionic surfactants, metal soaps, paraffins, talcum powder, polyethylene glycol, mixtures of ketones and fatty alcohols, and mixtures thereof.
  • Preferred types of compressing aids are nonionic surfactants and mixtures of ketones and fatty alcohols.
  • the compressing aid is present at a level of 0.5 - 5% by weight, preferably 1 - 3% by weight, based on the total weight of the detergent block.
  • the granulated builder material is mixed with the other components of the detergent block including the compressing aid to form a particulate mixture. Subsequently, said mixture is compressed in a mould under a pressure of 3 - 30 kN/cm 2 , preferably 3 - 15 N/cm 2 .
  • This compaction step can be carried out in a suitable press, preferably a hydraulic press, for instance a LAEIS
  • TYP HPF 630 Hydraulische Doppeldr ⁇ ckpresse, TYP HPF 630 as manufactured by LAEIS, West Germany.
  • more than one compaction cycle is applied in order to maximise the block density and quality.
  • the detergent block of the present invention contains from 15 - 70% by weight of a builder material granulated according to the process of the invention.
  • a builder material includes a non-phosphate builder and a co-ingredient.
  • This non-phosphate builder material is preferably selected from the group consisting of sodium nitrilotriacetate, sodium citrate, phosphonates, aluminosilicates, polycar- boxylates, layered silica, oxidised starch, polypeptides, oxidised heteropolymeric polysaccharides, salts of dipicolinic acid (DPA) , ethylene diamine tetraacetic acid (EDTA) , salts of terpolymers from acrylic acid, maleic acid and vinylacetate, 3 Na-salt of ethylglycine diacetic acid.
  • DPA dipicolinic acid
  • EDTA ethylene diamine tetraacetic acid
  • the most preferred types of non-phosphate builder material are sodium nitrilotriacetate, sodium citrate, and 3 Na-salt of methylglycine diacetic acid.
  • the detergent block of the invention contains, in addition to the above builder component, from 5 - 80% by weight, preferably from 10-70% by weight, of an alkaline agent, such as sodium- or potas ⁇ sium-hydroxide, -silicate, particularly -metasilicate, or -carbonate.
  • an alkaline agent such as sodium- or potas ⁇ sium-hydroxide, -silicate, particularly -metasilicate, or -carbonate.
  • compositions for use in a mechanical warewashing machine are most alkaline and contain the highest levels of these alkaline agents, which levels are suitably in the range of 20 - 70% by weight.
  • the detergent block of the invention may also comprise a bleach component, encapsulated or not, in an amount of up to 20% by weight.
  • Said bleach component may be a hypohalite bleach such as NaDCCA, or a peroxygen compound, i.e. a compound capable of yielding hydrogen peroxide in aqueous solution.
  • a peroxygen compound selected from alkali metal peroxides, organic peroxides, such as urea peroxide, and inorganic persalts such as the alkali metal perborates, percarbonates, perphosphates, per- silicates and persulphates, is preferably used. Mixtures of two or more of such compounds may also be suitable.
  • sodium perborate tetrahydrate and, especially, sodium perborate monohydrate.
  • Sodium perborate monohydrate is preferred because of its high active oxygen content.
  • Sodium percarbonate may also be preferred for environmental reasons.
  • the peroxygen bleach compound is suitably present in the detergent block of the invention at a level of up to 20% by weight, preferably of from 5 to 10 %by weight.
  • hypohalite bleach may be suitably used in an amount of up to 5%, preferably 1-4% by weight, as active chlorine.
  • Organic peroxyacids may also be suitable as peroxygen bleaching agent.
  • Such materials normally have the general formula:
  • R is an alkylene or substituted alkylene group containing from 1 to about 20 carbon atoms, optionally having an internal amide linkage; or a phenylene or substituted phenylene group; and Y is hydrogen, halogen, alkyl, aryl, an imido-aromatic or non-aromatic group, a C00H or
  • Typical monoperoxy acids useful herein include, for example:
  • peroxybenzoic acid and ring-substituted peroxybenzoic acids e.g. peroxy- ⁇ -naphthoic acid
  • aliphatic, substituted aliphatic and arylalkyl monoperoxyacids e.g. peroxylauric acid, peroxystearic acid and 6- (N-phthalimido) -peroxyhexanoic acid (PAP)
  • PAP peroxybenzoic acid and ring-substituted peroxybenzoic acids
  • Typical diperoxyacids useful herein include, for example:
  • inorganic peroxyacid compounds are suitable, such as for example potassium monopersulphate (MPS) . If organic or inorganic peroxyacids are used as the peroxygen compound, the amount thereof will normally be within the range of about 2-10 % by weight, preferably from 4-8 % by weight.
  • MPS potassium monopersulphate
  • All these peroxide compounds may be utilized alone or in conjunction with a peroxyacid bleach precursor and/or an organic bleach catalyst not containing a transition metal.
  • Peroxyacid bleach precursors are known and amply described in literature, such as in the British Patents 836988;
  • peroxyacid bleach precursors are those of the cationic i.e. quaternary ammonium substituted peroxyacid precursors as disclosed in US Patent 4,751,015 and 4,397,757, in EP-A0284292 and EP-A-331,229.
  • peroxyacid bleach precursors of this class are:
  • a further special class of bleach precursors is formed by the cationic nitriles as disclosed in EP-A-303,520 and in European Patent Specification No.'s 458,396 and 464,880.
  • peroxyacid bleach precursors can be used in the present invention, though some may be more preferred than others.
  • the preferred classes are the esters, including acyl phenol sulphonates and acyl alkyl phenol sulphonates; the acyl-amides; and the quaternary ammonium substituted peroxyacid precursors including the cationic nitriles.
  • Examples of said preferred peroxyacid bleach precursors or activators are sodium-4-benzoyloxy benzene sulphonate (SBOBS) ; N,N,N'N' -tetraacetyl ethylene dia ine (TAED) ; sodium-1-methyl-2-benzoyloxy benzene-4-sulphonate; sodium- 4-methyl-3-benzoloxy benzoate; SPCC; trimethyl ammonium toluyloxy-benzene sulphonate; sodium nonanoyloxybenzene sulphonate (SNOBS); sodium 3,5,5-trimethyl hexanoyloxyben- zene sulphonate (STHOBS) ; and the substituted cationic nitriles.
  • SBOBS sodium-4-benzoyloxy benzene sulphonate
  • TAED N,N,N'N' -tetraacetyl ethylene dia ine
  • TAED sodium-1-methyl-2
  • the precursors may be used in an amount of up to 12 %, preferably from 2-10 % by weight, of the composition.
  • Organic bleach catalyst most suitable for being utilized here are the so-called sulphonimides as disclosed in EP-A- 0453003 and EP-A-0446982.
  • the detergent block of the invention preferably also comprises up to 25% by weight of an anti-scaling agent, consisting of a polycarboxylated polymer and a carrier material therefore.
  • concentration of said polymer in said anti-scaling agent is preferably in the range of from 20 to 50% by weight as calculated on the total weight of the anti-scaling agent.
  • the anti-scaling agent is, preferably, substantially homogeneously mixed throughout the detergent block of the invention.
  • Suitable polymer materials for this anti-scaling agent may be the same as those of which the solution is suitable for use as co-ingredient in the granulating step of the present invention.
  • Suitable inorganic carrier materials are selected from the group consisting of sulphates, carbonates, silicates, aluminosilicates, percarbonates, perborates, clays, and mixtures thereof. Most preferred carrier material is selected from silicates, carbonates, and mixtures thereof.
  • the detergent block of the invention may further comprise suitable minor ingredients, such as bleach stabilizers, enzymes, etc.
  • Norasol LMW-45N 40% solution of sodium polyacrylate (mol wt: 4500) in water, ex NorsoHaas.
  • Example 1 Comparative Example A
  • Example no. 1 A (parts) (parts)
  • NTA-granules sodium nitrilotriacetate
  • the resulting powder was compressed to 3 kg blocks (having a density of 1710 kg/m 3 ) in a mould under a pressure of 12 kN/cm 2 using a double punch press.
  • Powder-form mixtures having the following compositions were obtained by mixing the components in a L ⁇ dige-type mixer:
  • NTA-granules were previously prepared by granulating 33.0 parts of Trilon A92 -with 0.75 parts of Crystal-112, and subsequently spraying the thus-prepared granulated material with 2.0 parts of Dehypon 2429.
  • the sprayed Trilon A92 shown in the composition of Example B was made by spraying 33.0 parts of of Trilon A92 with 2.0 parts of Dehypon 2429.
  • the resulting powder was compressed to 3 kg blocks (having a density of 1680 kg/m 3 )in a mould under a pressure of 12 kN/cm 2 using a double punch press.
  • NTA-granules (1) and NTA-granules (2) were prepared by granulating 33 parts of Trilon A92 with 1.67 parts respectively 2.78 parts of Norasol LMW 45N.
  • the moisture content of NTA-granules (1) is 3.41% by weight and of NTA-granules (2) is 5.01% by weight.
  • NTA-granules (1) 34 . 67 - NTA-granules (2) - 35 . 78 Dehypon 2429 2 . 00 2 . 00 Dequest 2047 0 .25 0 .25 Perborate mono 7 . 00 7 . 00 Caustic 47. 75 47 . 75 Norasol WL-2-Si 10 . 63 9 . 38
  • the resulting powder was compressed to 3 kg blocks (having a density of 1670 kg/m 3 ) in a mould under a pressure of 12 kN/cm 2 using a double punch press.
  • the blocks prepared by compressing the powder of Example 3 showed good quality and stability, whereas the blocks obtained from the powder of Example C showed lamination and were physically not stable.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Detergent Compositions (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
PCT/EP1996/000323 1995-02-17 1996-01-19 Solid detergent block WO1996025481A1 (en)

Priority Applications (7)

Application Number Priority Date Filing Date Title
JP52460496A JP3833252B2 (ja) 1995-02-17 1996-01-19 固体洗剤ブロック
CA002211229A CA2211229C (en) 1995-02-17 1996-01-19 Solid detergent block of compressed granular material
BR9607331A BR9607331A (pt) 1995-02-17 1996-01-19 Process para preparar um bloco de material granular comprimido e composição detergente sólida
EP96901771A EP0809689B1 (en) 1995-02-17 1996-01-19 Solid detergent block
AU46218/96A AU713237B2 (en) 1995-02-17 1996-01-19 Solid detergent block
DE69602086T DE69602086T2 (de) 1995-02-17 1996-01-19 Festes waschmittelstück
FI973347A FI973347A0 (fi) 1995-02-17 1997-08-15 Kiinteä pesuainekappale

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP95200381 1995-02-17
EP95200381.2 1995-02-17

Publications (1)

Publication Number Publication Date
WO1996025481A1 true WO1996025481A1 (en) 1996-08-22

Family

ID=8220022

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1996/000323 WO1996025481A1 (en) 1995-02-17 1996-01-19 Solid detergent block

Country Status (13)

Country Link
US (1) US5719111A (xx)
EP (1) EP0809689B1 (xx)
JP (1) JP3833252B2 (xx)
AU (1) AU713237B2 (xx)
BR (1) BR9607331A (xx)
CA (1) CA2211229C (xx)
DE (1) DE69602086T2 (xx)
ES (1) ES2130790T3 (xx)
FI (1) FI973347A0 (xx)
TR (1) TR199700798T1 (xx)
TW (1) TW331573B (xx)
WO (1) WO1996025481A1 (xx)
ZA (1) ZA96888B (xx)

Cited By (4)

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Publication number Priority date Publication date Assignee Title
WO2008000560A1 (de) * 2006-06-27 2008-01-03 Henkel Ag & Co. Kgaa Wasch- oder behandlungsmittelportion i
US9096820B2 (en) 2009-12-24 2015-08-04 Akzo Nobel Chemicals International B.V. Coated particles of a glumatic acid N,N-diacetate chelating agent
JP2016501980A (ja) * 2013-01-04 2016-01-21 エコラボ ユーエスエー インコーポレイティド 固体タブレット単位用量オーブン洗浄剤
EP1737940B1 (en) 2004-04-15 2019-11-06 Ecolab USA Inc. Binding agent for solidification matrix

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DE19543162A1 (de) * 1995-11-18 1997-05-22 Basf Ag Feste Textilwaschmittel-Formulierung aus anorganischen Buildern, Glycin-N,N-diessigsäure-Derivaten als organische Cobuilder sowie anionischen und nichtionischen Tensiden
JP3810847B2 (ja) * 1996-01-22 2006-08-16 花王株式会社 高密度粉末洗剤組成物
AU712844B2 (en) * 1996-06-19 1999-11-18 Diversey Ip International Bv Floor treating composition
DE19937345A1 (de) * 1999-08-11 2001-02-15 Basf Ag Mischpulver oder Mischgranulat auf Basis von Glycin-N,N-diessigsäure
GB2415695A (en) * 2004-07-02 2006-01-04 Reckitt Benckiser Nv Detergent composition comprising a chelating agent
GB0522659D0 (en) * 2005-11-07 2005-12-14 Reckitt Benckiser Nv Delivery cartridge
US7893012B2 (en) * 2007-05-04 2011-02-22 Ecolab Inc. Solidification matrix
EP2190969B1 (en) 2007-05-04 2014-08-20 Ecolab Inc. Pressed, self-solidifying, solid cleaning compositions and methods of making them
US8338352B2 (en) * 2007-05-07 2012-12-25 Ecolab Usa Inc. Solidification matrix
US7759300B2 (en) * 2007-07-02 2010-07-20 Ecolab Inc. Solidification matrix including a salt of a straight chain saturated mono-, di-, or tri- carboxylic acid
US8759269B2 (en) * 2007-07-02 2014-06-24 Ecolab Usa Inc. Solidification matrix including a salt of a straight chain saturated mono-, di-, and tri- carboxylic acid
US8889048B2 (en) 2007-10-18 2014-11-18 Ecolab Inc. Pressed, self-solidifying, solid cleaning compositions and methods of making them
US8138138B2 (en) * 2008-01-04 2012-03-20 Ecolab Usa Inc. Solidification matrix using a polycarboxylic acid polymer
US8198228B2 (en) * 2008-01-04 2012-06-12 Ecolab Usa Inc. Solidification matrix using an aminocarboxylate
US8772221B2 (en) * 2008-01-04 2014-07-08 Ecolab Usa Inc. Solidification matrices using phosphonocarboxylic acid copolymers and phosphonopolyacrylic acid homopolymers
US8951956B2 (en) * 2008-01-04 2015-02-10 Ecolab USA, Inc. Solid tablet unit dose oven cleaner
US8530403B2 (en) * 2009-11-20 2013-09-10 Ecolab Usa Inc. Solidification matrix using a maleic-containing terpolymer binding agent
US20110124547A1 (en) * 2009-11-23 2011-05-26 Ecolab Inc. Solidification matrix using a sulfonated/carboxylated polymer binding agent
US8802611B2 (en) * 2010-05-03 2014-08-12 Ecolab Usa Inc. Highly concentrated caustic block for ware washing
US9574163B2 (en) 2012-10-26 2017-02-21 Ecolab Usa Inc. Caustic free low temperature ware wash detergent for reducing scale build-up
US10184097B2 (en) * 2013-02-08 2019-01-22 Ecolab Usa Inc. Protective coatings for detersive agents and methods of forming and detecting the same
US9267096B2 (en) 2013-10-29 2016-02-23 Ecolab USA, Inc. Use of amino carboxylate for enhancing metal protection in alkaline detergents
US11377626B2 (en) * 2018-03-08 2022-07-05 Ecolab Usa Inc. Solid enzymatic detergent compositions and methods of use and manufacture

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TR199700798T1 (xx) 1998-01-21
DE69602086T2 (de) 1999-08-05
EP0809689A1 (en) 1997-12-03
AU4621896A (en) 1996-09-04
AU713237B2 (en) 1999-11-25
TW331573B (en) 1998-05-11
FI973347A (fi) 1997-08-15
EP0809689B1 (en) 1999-04-14
BR9607331A (pt) 1997-11-25
JP3833252B2 (ja) 2006-10-11
ZA96888B (en) 1997-08-05
CA2211229A1 (en) 1996-08-22
FI973347A0 (fi) 1997-08-15
US5719111A (en) 1998-02-17
DE69602086D1 (de) 1999-05-20
JPH11500154A (ja) 1999-01-06
ES2130790T3 (es) 1999-07-01
CA2211229C (en) 2007-01-09

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